INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Liying Xu,Zhenlei Wang,Saidi Wang,Yanrong Liu,Xingmei Lu,Bing Yang,Ke Wang,Lijun Han,Jiayu Xin,Suojiang Zhang
The electrochemical dimerization of acrylonitrile (AN) to adiponitrile (ADN) is an essential process for nylon-66 production, but this process still faces many challenges such as low energy conversion efficiency and poor selectivity. Herein, various ionic liquids (ILs) were used as electrolyte additives to evaluate their effects on the electrochemical dimerization of AN. The addition of IL significantly enhanced the performance of the electrolytic reaction and inhibited the hydrogen evolution reaction (HER). The electrolyte containing Tetrabutylphosphonium bromide (TBPB) showed the highest faraday efficiency of adiponitrile (FEADN) of 84.5% and excellent stability at an optimal current density of 200 mA cm–2. Molecular dynamics (MD) simulations revealed that TBPB was uniformly dispersed in the electrolyte and formed a “long brush” hydrophobic layer with appropriate wettability on the electrodes. Moreover, it was observed that ILs with a more symmetrical cationic structure exhibited a better hydrophobic layer effect, favoring the dimerization of AN to ADN.
研究领域:
化学工程
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材料科学
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产品关联
DOI
高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Jie Huang,Wenhao Yang,Sen Zhang,Jingjie Luo,Changhai Liang
Catalytic hydrogenation of adiponitrile to hexamethylenediamine (HMDA) via alkali-free processes is essential to produce high-value downstream chemicals. In this work, we synthesized a series of Co@C CNT x catalysts using CNT promotion to strength the carbon skeleton derived by ZIF-67. Compared to the Co@C without CNT promotion, great enhancement of HMDA yield was achieved by Co@C CNT x . Characterizations suggested that CNT in the precursor modified the crystallization of the active Co centers as well as the surface composition in the Co@C CNT x . Strong Co-carbon interaction was formed via Co-N coordination caused by the facilitated re-dispersion of N- containing functionalities. The ethanol contact angle on Co@C CNT x was changed for better mass transfer and diffusion of reaction liquid on the catalyst. As a final result, the oxidation of cobalt sites was greatly suppressed in Co@C CNT 0.3 and Co@C CNT 0.5 , which was proved an essential factor for their fast reaction rates. 88 % yield of HMDA with the rate of 4.5 mol HMDA /mol Co /h was reached under a much higher utilization rate of Co center.
研究领域:
化学工程
·
催化化学
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产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2016
·
IF 4.803
Shiyou Li,Dongni Zhao,Peng Wang,Xiaoling Cui,Fengjuan Tang
To satisfy the need of 5 V high-voltage cathode materials, lithium difluoro(oxalato)borate (LiDFOB) with excellent film-forming property has been chosen as lithium salt , and adiponitrile (ADN) with stable electrochemical performance has been evaluated as functional additive. An electrochemical investigation of this novel electrolyte solution shows a wide electrochemical oxidation window of nearly 6.0 V vs Li + /Li. Due to the positive effect of ADN on the cathode/electrolyte interface, LiNi 0.5 Mn 1.5 O 4 /Li half-cell with ADN-adding electrolyte exhibits prominent rate capability and cyclability. It is believed that the improvement of electrochemical performances has benefitted greatly from interfacial impedance reducing. Two modeling hypotheses have been used to explain interfacial interaction between ADN and LiNi 0.5 Mn 1.5 O 4 , by the means of analysis of X-ray photoelectron spectroscopy and theoretical calculation. Results show that ADN can enrich the surface of cathode material to hinder the further decomposition of the electrolyte, and contribute to the formation of a cathode-electrolyte interface passivation film with protective and conductive properties.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Yijing Qiu,Dongsheng Lu,Yunyan Gai,Yuepeng Cai
Adiponitrile (ADN) is studied as an additive of commercial carbonate electrolyte for a graphite/NCM811 Li-ion cell in this work. Compared with the cell using a baseline electrolyte, the cycling stability of the cells using 0.2, 0.5, 1, and 2 wt % ADN-added electrolytes is significantly improved. Among them, the effect is most prominent when the ADN content is 0.5 wt %, and the capacity retention rate of the cell after 200 cycles at 0.3 C is increased by 17.6%. Scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses confirm that ADN can make the coating layer formed on the cathode and anode surfaces of the cell denser and uniform. The formation of the cathodic coating layer does not obey the usual mechanism of adsorption between the nitrile group and metal ions, but it may be due to the polymerization of ADN initiated by carbocations from the oxidation of solvent molecules (ethylene carbonate/ethyl methyl carbonate) in the electrolyte. The cathodic coating layer greatly decreases the oxidation of the electrolyte so that a stable coating layer (also called solid electrolyte interface/SEI) can be formed on the anode, which is the reason for improvement of the cycling performance of the cell. However, the formation of the anode SEI layer is almost independent of ADN, and it still depends on the common reduction reaction of the electrolyte.
研究领域:
材料科学
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电化学
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DOI
高影响因子
AICHE JOURNAL
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2024
·
IF 3.5
Le Zhou,Xin Zhang,Yu Han,Xin Li,Ze-Quan Zeng,Hai-Kui Zou,Yong Luo
The Co@NC catalyst exhibits significant protic solvent preference for hydrogenation of nitriles to primary amines. However, the effect of mixed protic solvents on catalytic hydrogenation has received little attention. Herein, the synergetic solvent effect has been proposed to accelerate the hydrogenation of adiponitrile (ADN) to hexamethylenediamine through H 2 O-ethanol hydrogen bond networks on Co@NC catalyst. Experimental screenings on solvents showed that ADN conversion in H 2 O-ethanol was 1.6 ~ 5.1 times greater than in single solvents. Kinetic models in H 2 O/ethanol ( v W = 0.6), H 2 O, and ethanol showed that the solvents effected on H 2 transformation dominated the reaction. Isotope labelling and kinetic experiments revealed that H 2 O and ethanol acted as co-catalysts through exchanging and transferring hydrogen via hydroxyl groups. Density functional theory calculations confirmed that the energy barrier for proton transfer mediated by H₂O–ethanol was reduced by 0.18 eV compared to proton transfer mediated by H₂O–H₂O dimers.
研究领域:
催化化学
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材料科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Tao Guo,Fang-You Yan,Yao-Feng Wang,Xiao-Feng Xu,Qing-Zhu Jia,Bao-Hua Xu
To reach highly active and selective gas-phase nitrilation of dimethyl adipate (DMA) with NH 3 , a series of Nb x W 10-x (x = 10, 9, 7, 5 and 0) composite were fabricated by a sol–gel method to approach the homogeneous combination of NbO x and WO x . As a result, the single-pass yield of adiponitrile (ADN) reached 85.2% over Nb 9 W 1 under lower reaction temperature and lower NH 3 /DMA molar ratio. Consequently, the space–time yield (STY) of ADN over Nb 9 W 1 was 1.7 ∼ 30 times higher than that of previous catalysts. Mechanistic experiments demonstrated the activity strongly correlates the interaction between the carbonyl functionality and the composite. Further, a significant synergistic effect between W and Nb was disclosed, wherein the Nb-based domains account for activating DMA while the W-based domains mainly adsorb and activate NH 3 feedstock.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Yuqin Zhu,Hang Gao,Lei Huang,Yang Lv,Pingle Liu
In the present study, the catalyst modified with alkaline oxide can enhance the selectivity to primary amines. However, the addition of alkaline oxide inevitably reduces catalytic activity. In this study, NiCo-NC@BaO-MFC catalyst derived from zeolitic imidazolate framework-67, Ba(CH 3 COO) 2 , and melamine formaldehyde (MF) resin was prepared and used for the hydrogenation of adiponitrile (ADN) to hexamethylene diamine (HDMA). The carbon layer obtained from the MF resin effectively prevents the interaction between barium (Ba) and the active center, thus improving target product selectivity without decreasing catalytic activity. The results of the density functional theory (DFT) calculation and characterization indicated that the effect of synergy between nickel (Ni) and cobalt (Co) bimetals induces an electron density growth on the Ni surface, bringing the d-band center toward the Fermi surface. Meanwhile, the high electron density of the active center compensates for the electron-deficient state of the carbon atom in –C N, thus improving the catalytic activity. Furthermore, it was found that the introduction of Ba promotes the formation of nucleophilic hydrogen anions, which facilitates the hydrogenation of 6-aminohexylimine (AHIM) to HDMA and inhibits the intramolecular condensation of AHIM, hence improving the selectivity to HDMA. The NiCo-NC@BaO-MFC catalyst gives 98.6 % ADN conversion and 97.2 % selectivity to HDMA in an alkali-free system.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
PubMed
高影响因子
Catalysts
·
2022
·Vol. 12
·期 7
·694
·
IF 4.501
Ji Qi,Ziying An,Xiao Chen,Chuang Li,Yan Du,Xiuhong Zhang,Changhai Liang
The classic acrylonitrile (AN) electrohydrodimerization (EHD) to adiponitrile (ADN) process produces oxygen on the anode side. The oxygen evolution reaction (OER) is energy consuming, and O2is of low value and has security issues while directly contacting with organic molecules. Herein, by replacing OER with 5-hydroxymethylfurfural oxidation reaction (HMFOR), we report paired electrolysis of AN and HMF for simultaneous generation of ADN and 2,5-furandicarboxylic acid (FDCA). On the anode side, the electrodeposited amorphous NiMoP film-covered nickel foam efficiently boosted HMFOR activity by enlarging the electrochemically active surface area (ECSA) via in situ selective removal of Mo and P on the surface. On the cathode side, addition of dimethylformamide (DMF) as a cosolvent enhanced the reaction efficiency of ANEHD by forming a single-phase electrolyte that offers better interaction between AN and the electrode. The ANEHD–HMFOR paired system shows excellent generation rates of FDCA (0.018 gFDCA·h−1·cm−2) and ADN (0.017 gADN·h−1·cm−2) at a high cell current (160 mA). An amount of 1 kWh of electricity can produce 2.91 mol of ADN and 0.53 mol of FDCA with 107.1% Faraday efficiency.Keywords:paired electrolysis;5-hydroxymethylfurfural oxidation;acrylonitrile electrohydrodimerization;adiponitrile;2,5-furandicarboxylic acid;dimethylformamide cosolvent
研究领域:
化学工程
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电化学
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DOI
高影响因子
ACS Omega
·
2020
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IF 2.87
Li Wang,Shengxian Liu,Wenjing Du,Tongyi Dou,Changhai Liang
5-Cyanovaleramide (5-CVAM) is an important intermediate of a herbicide and chemical raw material. Herein, we found a novel nitrile hydratase from the strain Rhodococcus erythropolis CCM2595, exhibiting high regioselectivity with higher substrate specificity toward dinitriles than mononitriles. In the past, the strain was shown to degrade only phenol, hydroxybenzoate, p-chlorophenol, aniline, and other aromatic compounds. In our study, 20 mM adiponitrile was completely consumed within 10 min with 95% selectivity to 5-CVAM and 5% selectivity to adipamide. In addition to its high regioselectivity, our recombinant Escherichia coli showed a higher substrate tolerance of up to 200 mM adiponitrile even after 3 h when compared with two reported strains with their cyano-tolerance concentrations of up to 100 mM, which is considered to be the highest cyano-tolerance. Such a robust biocatalyst is a desirable attribute of a biocatalyst intended for use in commercial applications of 5-CVAM.
研究领域:
生物催化
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生物化学
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化学工程
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酶技术
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产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Guang-Rong Ding,Yao-Feng Wang,Guo-Yi Duan,You-Qian Fan,Bao-Hua Xu
In this study, a tungstated zirconia (WOx/ZrO2) catalyst was developed for the continuous synthesis of adiponitrile (ADN) by gas-phase nitrilation of dimethyl adipate (DMA) with NH3. The highest TOFADN could be reached on WOx/ZrO2 bearing ∼1D WOx species (highly dispersed and discontinuous status) at the surface, which, however, delivered the poorest selectivity toward nitrilation (SADN+MCP). In comparison, both efficient and selective transformation of DMA to ADN was achieved by fabricating WOx/ZrO2 with continuously distributed oligomeric WOx species (∼2D) at the surface, either by varying the dosage of the W-reagent in the preparation of WOx(m)/ZrO2 or by doping a proper amount of the Mn element into WOx(5.0)/ZrO2, bearing WO3 NPs. Furthermore, the in situ diffuse reflectance infrared Fourier transform spectroscopy investigations of both independent and competitive adsorptions of ester functionality and NH3 over W–O–Zr, W–O–W, and Zr–O–Zr boundaries at the surface clarified the synergistic effect of these species in the activation of DMA/NH3 and thereby nitrilation.
研究领域:
催化
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化学工程
·
表面科学
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产品关联
DOI
PubMed
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2023
·
IF 5.2
Yankun Xie,Lukun Feng,Dongdong Li,Yin Tang,Caizhen Zhu,Mingliang Wang,Jian Xu
In this work, a novel type of highly Li + -ions conductive, nonflammable adiponitrile (ADN)-based gel polymer electrolyte (denoted as AT11-GF) was prepared as a promising solid-state electrolyte for lithium (Li)-metal batteries by in-situ polymerization method. In order to overcome the parasitic reactions of ADN and triethyl phosphate (TEP) on Li-anode surface, fluoroethylene carbonate (FEC) was utilized as film-forming agent to generate LiF-enrich interface in this system of ADN-based electrolyte. The as-prepared electrolyte exhibited high ionic conductivity of 1.724 × 10 −3 S/cm at ambient temperature, wide electrochemical window (∼5.75 V vs. Li + /Li), favorable Li + -ion transfer number ( t Li + =0.70), and superior interfacial compatibility with Li anode (ultra-stable at a current density of 0.2 mA/cm 2 for 1000 h). The LiFePO 4 |AT11-GF|Li battery presented an excellent rate capacity of 116.9 mAh/g at 2.0 C, and long-term cycling performance with a specific capacity of 134.6 mAh/g and a capacity retention of 94.5% after 1000 cycles at a current density of 1.0 C. Therefore, this as-prepared ADN-based electrolyte exhibited great promise for the application in solid-state Li-metal batteries.
研究领域:
材料科学
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能源技术
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产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 14
·9307-9318
·
IF 12.732
Tianle Zheng,Jianwei Xiong,Bingying Zhu,Xiaotang Shi,Ya-Jun Cheng,Hongbin Zhao,Yonggao Xia
Lithium secondary batteries (LSBs) have witnessed explosive growth in the last decade. A wide operating temperature window is crucial for practical applications. A new concept is developed to expand the temperature window between −20 °C and 150 °C, where a competitive decomposition process between the electrolyte and solvent is manipulated with adiponitrile (ADN) over a wide temperature range. The decomposition of ethylene carbonate (EC) solvent and anions of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium oxalyldifluoroborate (LiODFB) is regulated with ADN via a temperature-dependent lithium solvation mechanism. As a result, a SEI layer with a rich inorganic component is formed at elevated temperatures, leading to improved performance in lithium titanate (LTO)/Li, lithium iron phosphate (LFP)/Li, and LiNi0.5Co0.2Mn0.3O2 (NCM523)/Li batteries over a wide temperature range. It enables a coulombic efficiency (CE) of 97.39% at 100 °C and more than 100 hours of cycling of Li/Li batteries at 150 °C, as well as stable cycling of LFP/Li batteries in the temperature range between 120 °C and −20 °C. Stable cycling performance is demonstrated with the LTO/Li batteries over a wider temperature range from −40 °C to 150 °C. High-temperature electrochemical stability is exhibited at 5C, with a capacity retention ratio of 87.94% at 120 °C and 99.93% at 100 °C after 1000 cycles.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）